Modified alkyl-phenol-aldehyde resins, use thereof as additives for improving the properties of liquid hydrocarbon fuels in cold conditions

ABSTRACT

Modified alkylphenol-aldehyde resins include one or more alkylamines, having preferably at least one primary amine type group as well as their use for improving the flow properties of motor fuels and hydrocarbon fuels, such as in particular jet fuel, gas oil, fuel oil domestic, heavy fuel oil.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a National Phase Entry of International ApplicationNo. PCT/IB2011/055863, filed on Dec. 21, 2011, which claims priority toFrench Patent Application Serial No. 1061193, filed on Dec. 23, 2010,both of which are incorporated by reference herein.

BACKGROUND AND SUMMARY

The present invention relates to novel alkylphenol-aldehyde resins whichcan be used in particular as wax anti-settling additives for oils andoil distillates and in particular for motor fuels and liquid hydrocarbonfuels.

The alkylphenol-aldehyde resins originating from the condensation ofalkyl phenol and aldehyde have been known for a long time as agents forimproving the flow of mineral oils. See for example, EP 311 452 whichdescribes condensation products of at least 80% mol of dialkylphenolsand aldehydes having 1 to 30 carbon atoms; EP 857 776 which describesthe use of alkylphenol-aldehyde resins in which the alkyl groups ofalkylphenol have 4 to 12 carbon atoms and the aldehyde has 1 to 4 carbonatoms and containing no more than 10% mol of alkylphenols having morethan one alkyl group, in combination with ethylene/vinyl ester co- orter-polymers for improving the fluidity of mineral oils; and EP 1 584673 which describes alkylphenol-aldehyde resins of Mn between 1000 and3000 originating from the condensation of a C1-C4 aldehyde and a mixtureof alkylphenols with a majority of monoalkylphenol, the alkyl grouphaving 1 to 20 carbon atoms intended to improve the low temperature flowproperties of motor fuel compositions. Modified alkylphenol-aldehyderesins have also been proposed as additives for improving the lowtemperature flow of mineral oils; EP 1 767 610 describes alkylphenolresins, the condensation reaction of which with the aldehydes is carriedout in the presence of fatty acids having 2 to 50 carbon atoms, or theirderivatives, such as esters.

The present invention proposes novel modified alkylphenol-aldehyderesins which can be used for improving the low temperature stability ofmotor fuels and liquid hydrocarbon fuels and more particularly the lowtemperature flow by limiting the settling of waxes contained in themotor fuels and liquid fuels. The modified alkylphenol-aldehyde resinsaccording to the invention can be obtained by a Mannich reaction of analkylphenol-aldehyde condensation resin

-   -   with at least one aldehyde and/or one ketone having 1 to 8        carbon atoms, preferably having 1 to 4 carbon atoms;    -   and at least one hydrocarbon compound having at least one        alkylmonoamine or alkylpolyamine group (i.e. having several        amine groups) having between 4 and 30 carbon atoms, called        hereafter alkylamine,

the alkylphenol-aldehyde condensation resin can itself be obtained bycondensation

-   -   of at least one alkylphenol substituted by at least one linear        or branched alkyl group having 1 to 30 carbon atoms, preferably        a monoalkylphenol,    -   with at least one aldehyde and/or one ketone having 1 to 8        carbon atoms, preferably 1 to 4 carbon atoms.

The alkylphenol-aldehyde resins are known per se. According to apreferred embodiment, the modified alkylphenol-aldehyde resins accordingto the invention can be obtained from at least one alkylphenolsubstituted in para position; preferably at least nonylphenol. Theaverage number of phenolic nuclei per molecule of preferrednonylphenol-aldehyde resin is preferably superior to 6 and inferior orequal to 25, more preferably comprised within the range 8 to 17, andadvantageously within the range 9 to 16 phenolic nuclei per molecule.The average number of phenolic nuclei per molecule can be determined byRMN or GPC.

According to a preferred embodiment, the modified alkylphenol-aldehyderesins according to the invention can be obtained from at least onealdehyde and/or one ketone chosen from formaldehyde, acetaldehyde,propionaldehyde, butyraldehyde, 2-ethyl hexanal, benzaldehyde, acetone,preferably at least formaldehyde. According to a preferred embodiment,the modified alkylphenol-aldehyde resins according to the invention canbe obtained from at least one alkylamine having at least one primaryamine group, and advantageously at least one compound, all the aminegroups of which are primary amines. According to a preferred embodiment,the modified alkylphenol-aldehyde resins according to the invention canbe obtained from at least one alkylamine with an aliphatic chain havingbetween 12 and 24 carbon atoms, preferably between 12 and 22 carbonatoms. According to a particularly preferred embodiment, the modifiedalkylphenol-aldehyde resins according to the invention can be obtainedfrom at least one alkylamine having at least one primary amine group andcomprising an aliphatic chain having between 12 and 24 carbon atoms,preferably between 12 and 20 carbon atoms.

The commercially-available alkylamines are in general not pure compoundsbut mixtures. Among the commercially-available alkylamines which aresuitable, there can in particular be mentioned the following alkylamineswith an aliphatic chain marketed under the names: Noram®, Duomeen®,Dinoram®, Trinoram®, Triameen®, Armeen®, Polyram®, Lilamin® andCemulcat®. The viscosity of the modified alkylphenol-aldehydecondensation resins according to the invention diluted with 30% by massof aromatic solvent measured at 50° C. using a dynamic rheometer with ashear rate of 100 s⁻¹ is in general comprised between 1,000 and 10,000mPa·s, preferably between 1,500 and 6,000 mPa·s, and advantageouslybetween 2,500 and 5,000 mPa·s.

The modified alkylphenol-aldehyde resins according to the invention canbe used as additives for improving the low temperature properties offuel oils and of oil distillates of petroleum origin and/or of renewableorigin, and more particularly of the middle distillates the boilingtemperature range of which is in the majority comprised between 100 and500° C. Crude oils and the middle distillates, obtained from crude oilsof petroleum origin by distillation, such as gas oil, diesel motor fuelor fuel oil domestic, contain, depending on the origin of the crude oil,different quantities of n-alkanes or n-paraffins which by lowering thetemperature, typically below 0° C., crystallize out as lamellar crystalswhich have tendency to agglomerate: there is then a deterioration in theflow characteristics of the oils and distillates; difficulties occurduring transport, storage and/or use of the oil or fuel: the waxcrystals having tendency to block pipes, fuel lines, pumps and filters,for example in automobile vehicle fuel systems.

In winter or in conditions of use of the oil or the distillate at atemperature below 0° C., the crystallization phenomena can lead todeposits on the pipe walls, even a complete blockage. These problems arewell known in the field of motor fuels and liquid hydrocarbon fuelswhere numerous additives or mixtures of additives have been proposed andare marketed for reducing the size of the wax crystals and/or changingtheir shape and/or preventing their formation. The smallest possiblecrystal size is preferred as it minimizes the risks of blockage orclogging the filter. The usual agents for improving the flow of crudeoils and middle distillates are co- and ter-polymers of ethylene andvinyl and/or acrylic ester(s) alone or in a mixture with low molecularweight oil-soluble compounds or polymers which contain one or moreester, amide, imide, ammonium groups substituted by at least one alkylchain.

Apart from improving the flow of the oil and the distillate, anotherpurpose of the additives for improving the flow is to ensure thedispersion of the wax crystals so as to delay or prevent the settling ofthe wax crystals and therefore the formation of a layer rich in waxes atthe bottom of receptacles, vessels or storage tanks; these additives fordispersing waxes are called WASA (acronym for the term wax anti-settlingadditive). The inventors have noted that the modifiedalkylphenol-aldehyde resins according to the invention have a waxdispersing activity: they make it possible to limit the settling of thecrystallized waxes without further addition of dispersing agent. Thus amixture of co- and/or ter-polymer(s) of ethylene and vinyl ester(s)and/or acrylic ester(s) with at least one modified alkylphenol-aldehyderesin which is a subject of the invention makes it possible to avoid thesettling of wax crystals at low temperature.

The modified alkylphenol-aldehyde resins according to the invention canbe used for improving the low temperature behaviour and in particularthe dispersion of the waxes in motor fuels and liquid fuels based onhydrocarbon oils and middle distillates the range of boilingtemperatures of which is in the majority comprised between 100 and 500°C. In particular the motor fuels and liquid fuels to which the modifiedalkylphenol-aldehyde resins according to the invention are added are forexample jet fuel, gas oil or motor diesel fuel, fuel oil domestic, heavyfuel oil which have a boiling range from 120 to 500° C., preferably 140to 400° C. In general the sulphur content of the compositions of motorfuels and liquid fuels is less than 5,000 ppm, preferably less than 500ppm, and more preferentially less than 50 ppm, even less than 10 ppm andadvantageously with no sulphur, in particular for the motor fuels of gasoil and jet type.

Another object of the present invention is compositions of motor fuelsand liquid hydrocarbon fuels the boiling temperatures range of which isin the majority comprised between 100 and 500° C. comprising:

a majority proportion of hydrocarbon compounds and/or vegetable and/oranimal oils and/or their esters of oils and/or biodiesels of animaland/or vegetable origin

and a minority proportion, preferably comprised between 5 and 5,000 ppmby mass of at least one of the resins according to the invention.

The motor fuels and liquid fuels comprise the middle distillates with aboiling temperature comprised between 100 and 500° C.; their initialcrystallization temperature ICT is often greater than or equal to −20°C., in general comprised between −15° C. and +10° C. These distillatescan for example be chosen from the distillates obtained by directdistillation of crude hydrocarbons, the distillates from vacuumdistillation, hydrotreated distillates, distillates originating fromcatalytic cracking and/or hydrocracking of distillates under vacuum,distillates resulting from conversion processes of ARDS (atmosphericresidue desulphuration) type and/or visbreaking, distillates originatingfrom upgrading of Fischer-Tropsch cuts, distillates resulting from BTL(biomass to liquid) conversion of vegetable and/or animal biomass,and/or their mixtures. The motor fuels and liquid fuels can also containdistillates originating from refining operations which are more complexthan those originating from the direct distillation of the hydrocarbonswhich can for example originate from cracking, hydrocracking and/orcatalytic cracking processes and visbreaking processes.

The motor fuels and liquid fuels can also contain new sources ofdistillates, among which there can in particular be mentioned:

-   -   the heaviest cuts originating from the cracking and visbreaking        processes with a high concentration of heavy paraffins,        comprising more than 18 carbon atoms,    -   synthetic distillates originating from the conversion of gas        such as those originating from the Fischer Tropsch process,    -   synthetic distillates resulting from the treatment of biomass of        vegetable and/or animal origin, such as in particular NExBTL,    -   and the vegetable and/or animal oils and/or their esters such as        methyl or ethyl esters of vegetable oils (MEVO, EEVO),    -   hydrotreated and/or hydrocracked and/or hydrodeoxygenated (HDO)        vegetable and/or animal oils,    -   or also biodiesels of animal and/or vegetable origin.        These new motor fuel and fuel bases can be used alone or in a        mixture with standard petroleum middle distillates as a motor        fuel base and/or fuel oil domestic base; they generally comprise        long paraffin chains greater than or equal to 10 carbon atoms        and preferably C14 to C30.

According to an embodiment of the invention, the modifiedalkylphenol-aldehyde resins according to the invention are used in motorfuels and liquid fuels in combination with at least one additiveimproving the low-temperature flow, such as the co-polymers andter-polymers of ethylene and vinyl and/or acrylic ester(s). By way ofexample of additives improving the low-temperature flow of copolymertype, there can be mentioned the EVAs (copolymers of ethylene and vinylacetate); as examples of ter-polymers, there can be mentioned thosewhich are described in EP 1 692 196, WO09/106,743, WO09/106,744.According to an embodiment of the invention, the modifiedalkylphenol-aldehyde resins according to the invention can be used incombination with at least one wax-dispersing additive different from themodified alkylphenol-aldehyde resins according to the invention. Amongthe wax-dispersing additives, there can be mentioned the polarnitrogenous compounds.

According to a preferred embodiment, the modified alkylphenol-aldehyderesins according to the invention are used in motor fuels and liquidfuels without the addition of dispersant, chosen for example from thepolar nitrogenous compounds. According to a preferred embodiment, themodified alkylphenol-aldehyde resins according to the invention are usedin combination with at least one wax-dispersing additive different fromthe modified alkylphenol-aldehyde resins according to the invention,such as for example an unmodified alkylphenol-aldehyde resin andoptionally with at least one additive improving the low-temperatureflow.

According to a preferred embodiment, each additive separately or themixtures of additives are dissolved or dispersed with one or moresolvent or dispersing agents before adding to the oils or thedistillates. Solvent or dispersing agents are for example aliphaticand/or aromatic hydrocarbons or mixtures of hydrocarbons, for examplefractions of gasoline, kerosene, decane, pentadecane, toluene, xylene,and/or ethylbenzene and/or mixtures of commercial solvents such asSolvarex 10, Solvarex LN, Solvent Naphtha, Shellsol AB, Shellsol D,Solvesso 150, Solvesso 150 ND, Solvesso 200, Exxsol, ISOPAR. Polardissolution adjuvants, such as 2-ethylhexanol, decanol, isodecanoland/or isotridecanol can also be added.

Apart from the additives mentioned in the embodiments above, namely themodified alkylphenol-aldehyde resins according to the invention, theadditives for improving the low-temperature flow, the wax-dispersingadditives, other additives can also be added such as corrosioninhibiting agents, detergent additives, anti-clouding agents, additivesimproving the conductivity, colorants, reodorants, lubricity orlubricating additives, etc. Among these other additives, there can beparticularly mentioned:

a) the procetane additives, in particular (but not limitatively) chosenfrom the alkyl nitrates, preferably 2-ethyl hexyl nitrate, the aroylperoxides, preferably benzyl peroxide, and alkyl peroxides, preferablydi ter-butyl peroxide;

b) the anti-foam additives, in particular (but not limitatively) chosenfrom the polysiloxanes, the oxyalkylated polysiloxanes, and the fattyacid amides originating from vegetable or animal oils; examples of suchadditives are given in EP 663 000, and EP 736 590;

c) the detergent and/or anti-corrosion additives, in particular (but notlimitatively) chosen from the group constituted by the amines,succinimides, alkenylsuccinimides, polyalkylamines, polyalkyl polyaminesand polyetheramines; examples of such additives are given in EP 938 535.

d) lubricity additives or anti-wear agent, in particular (but notlimitatively) chosen from the group constituted by the fatty acids andtheir ester or amide derivatives, in particular glycerol monooleate, andmono- and polycyclic carboxylic acid derivatives; examples of suchadditives are given in the following documents: EP 680 506, EP 860 494,WO 98/04656, EP 915 944, FR 2 772 783, FR 2 772 784.

e) the cloud point additives, in particular (but not limitatively)chosen from the group constituted by the long-chain olefin/(meth)acrylicester/maleimide terpolymers, and fumaric/maleic acid ester polymers.Examples of such additives are given in EP 71 513, EP 100 248, FR 2 528051, FR 2 528 423, EP 112 195, EP 1 727 58, EP 271 385, EP 291 367;

f) anti-settling additives and/or wax dispersants in particular (but notlimitatively) chosen from the group constituted by (meth)acrylicacid/polyamine-amidified alkyl(meth)acrylate copolymers, polyaminealkenylsuccinimides, the derivatives of phthalamic acid and ofdouble-chain fatty amine; alkylphenol/aldehyde resins that differ fromthe alkylphenol/aldehyde resins according to the invention; Examples ofsuch additives are given in EP 261 959, EP 593 331, EP 674 689, EP 327423, EP 512 889, EP 832 172; U.S. Patent Publication No. 2005/0223631;U.S. Pat. No. 5,998,530; WO 93/14178;

g) the cold operability multi-functional additives chosen from the groupconstituted by the polymers based on olefin and alkenyl nitrate asdescribed in EP 573 490;

h) other additives improving resistance to cold and filterability (CFI),such as the EVA and/or EVP copolymers;

i) anti-oxidants of hindered phenolic type or amines of alkylatedparaphenylene diamine type;

j) metal passivators, such as triazoles, alkylated benzotriazoles;

k) metal sequestering agents such as disalicylidene propane diamine(DMD)

l) acidity neutralizers such as cyclic alkylamines;

These other additives as well as the modified alkylphenol-aldehyderesins according to the invention are in general added in a quantityranging from 5 to 1,000 ppm (each)

DETAILED DESCRIPTION Example 1 Synthesis of ModifiedAlkylphenol-Aldehyde Resins by a Mannich Reaction

In a first stage, several alkylphenol-aldehyde resins are prepared bycondensation of para-nonylphenol and formaldehyde (for example accordingto the operating method described in EP 857 776) with viscosities at 50°C. (measured at 50° C. using a dynamic rheometer with a shear rate of 10s⁻¹ on the resin diluted with 30% by mass of aromatic solvent (Solvesso150) comprised between 1,800 and 4,800 mPa·s. In a second stage, thealkylphenol-aldehyde resins originating from the first stage aremodified by a Mannich reaction by the addition of formol and primaryalkyl(poly)amine (for example an alkylpolyamine having a C12 alkyl chain(marketed under the name Noram® C) for the resin (1 A)).

The characteristics of the resins obtained are shown in the table 1below: alkylamine used, amount of dry material, viscosity at 50° C.(measured on resin diluted with 30% by mass of Solvesso 150, shear rate10 s⁻¹).

TABLE 1 Average number Dry material Viscosity at of phenolic alkylamine(1 g-30 min- 50° C. nuclei per Resin N° used 200° C) (mPa · s) resinmolecule 1A Noram C 72.2% 3700 8.0 2A Trinoram S 70.30% 3675 4.1 2BTrinoram S 70.20% 1950 1.4 2C Trinoram S 70.10% 4855 14.1 2D Trinoram S69.80% 4590 16.5 2E Trinoram S 69.00% 3180 10.1 2F Trinoram S 70.10%4990 15.5 3A Noram SH 72.80% 2485 3.7

Example 2 ARAL Sedimentation Tests

Each of the modified alkylphenol resins of Example 1 are evaluated asanti-settling additive or WASA alone (i.e. not combined with anotherWASA dispersing constituent) in a gas oil (GOM 1) to which is added 300ppm by mass of a CFPP additive which is an EVA in solution at 70% bymass in an aromatic solvent (Solvesso 150 type) marketed under the nameCP7936C. Each modified alkylphenol resin is incorporated in the gas oilat a concentration of 70 ppm by mass (the resin being dissolved with 30%by mass of solvent, 100 ppm by mass of solution at 70% of activesubstance is used). By way of comparison, the gas oil GOM 1 to which isadded 300 ppm of the CFPP additive described previously and theunmodified alkylphenol-aldehyde resin (comparative resin 1 with aviscosity measured at 50° C. using a dynamic rheometer diluted with 30%by mass Solvesso 150 equal to 2,000 mPa·s) are also evaluated.

The anti-settling properties of the additives are evaluated by thefollowing ARAL settling test: 500 mL of middle distillate additives arecooled in a 500 mL test tube in a climatic chamber to −13° C. accordingto the following temperature cycle: passing from +10° C. to −13° C. in 4h then isothermal at −13° C. for 16 h. At the end of the test, a visualscore of the appearance of the sample and the volume of the settledphase is carried out, then the 20% constituting the volume at the bottomis taken out, for determination of cloud point CP (NF EN 23015) and CFPP(NF EN 116). Then the difference in the CP and CFPP is compared beforeand after settling (i.e. on the 20% volume at the bottom of the testtube), the lower difference, the better the performance of the CP, CFPPproperty measured.

The results are shown in Table 2 below.

TABLE 2 Volume of sediments CFPP measurement CP measurement (mL for (°C.) (° C.) Added resin 500 mL of NF EN 116 NF EN 23015 N^(o) sample)Visual score Before After Difference Before After Difference — −16Comparative 115 slightly cloudy −16 −4 −12 −6 4 −10 Resin 1 Resin 1A 90cloudy −18 −9 −9 −5 0 −5 Resin 2A 35 cloudy −19 −10 −9 −6 −2 −4 Resin 2B50 cloudy −19 −13 −6 −6 −2 −4 Resin 2C 0 homogeneous −18 −19 1 −6 −6 0Resin 3A 105 slightly cloudy −18 −4 −14 −6 3 −9

It is noted that the unmodified standard alkylphenol resin (comparativeresin 1) is not effective as regards anti-settling when it is used alone(i.e. without the addition of dispersant) whereas the modifiedalkylphenol resins according to the invention are, the most effectivebeing the resin 2C, containing tallow dipropylenetriamine, particularlypreferred. New ARAL sedimentation tests are carried out with the samegas oil of which the additivation rate of CFPP additive is unchanged(300 ppm) but for which the additivation rate of modifiedalklphenol-aldehyde resin (resin 2C) is different; once again, themodified alkylphenol-aldehyde resin is added in a solution concentratedto 70% by mass of active substance (resin) in 30% of solvent. By way ofcomparison, the gas oil GOM 1 to which is added 300 ppm of the CFPPadditive described previously and an unmodified alkylphenol-aldehyderesin (comparative resin 1) combined with a nitrogenous polar dispersantof amidified dodecenylsuccinic anhydride type with a tallowdipropylenetriamine.

The mixture of additives contains 20% by mass of resin 1 and 80% by massof polar amidified dodecenylsuccinic anhydride dispersant with a tallowdipropylenetriamine. The results are shown in Table 3 below.

TABLE 3 Resin added (ppm of Test tube solution at visual score CFPPmeasurement CP measurement WASA 70% m of (volume of (° C.) (° C.)additive(s) active sediments in mL on NF EN 116 NF EN 23015 usedsubstance) 500 mL of sample) Before After Difference Before AfterDifference No WASA 0 −16 Resin 2C 75 <5 homogeneous −20 −17 −3 −6 −6 0comparative 75 <10 homogeneous −18 −17 −1 −7 −6 −1 Resin 1 + dispersantResin 2C 50 10 −19 −17 −2 −6 −6 0 comparative 50 <10 homogeneous −20 −19−1 −7 −6 −1 Resin 1 + dispersant Resin 2C 25 10 homogeneous −18 −18 0 −6−6 0 comparative 25 125 Cloudy at the −18 −9 −9 −6 1 −7 Resin 1 + bottomdispersant Resin 2C 15 15 homogeneous −18 −19 1 −6 −5 −1 comparative 15115 Cloudy at the −16 −7 −9 −6 1 −7 Resin 1 + bottom dispersant

These results relating to the effectiveness of anti-settling as afunction of concentration (of active substance) show that the modifiedalkylphenol resin 2C according to the invention is more effective thanthe combination of standard alkylphenol resin+dispersant (polarnitrogenous compound) below 50 ppm of active substance. New ARALsedimentation tests are carried out with the resin 2C in 2 other enginegas oils (GOM 2 (gas oil of type B5, i.e. containing 5% by volume ofMEVO) and GOM 3 (gas oil of type B0 without MEVO) the characteristics ofwhich are shown in Table 6 below. By way of comparison, theanti-settling effectiveness of an unmodified alkylphenol-aldehyde resin(comparative resin 1) combined with a polar nitrogenous compounddispersant of dodecenylsuccinic anhydride type with a tallowdipropylenetriamine is evaluated; the results are shown in Tables 4(tests in GOM 2) and 5 (tests in GOM 3)

TABLE 4 evaluation in GOM 2 Resin added (ppm of solution at Test tubeCFPP measurement CP measurement WASA 70% m of visual (° C.) (° C.)additive(s) active score NF EN 116 NF EN 23015 used substance) 500 mLBefore After Difference Before After Difference comparative 112.5 100−27  −10 17 −4 1 5 Resin 1 + dispersant Resin 2C 112.5 <5 −21* −16 5 −4−4 0 *hard point at −16° C.

TABLE 5 evaluation in GOM 3 Resin added (ppm of solution at Test tubeCFPP measurement CP measurement WASA 70% m of visual (° C.) (° C.)additive(s) active score NF EN 116 NF EN 23015 used substance) 500 mLBefore After Difference Before After Difference comparative 100 0 −19−19 0 −7 −7 0 Resin 1 + dispersant Resin 2C 100 <5 −19 −18 1 −7 −7 0

TABLE 6 GOM GOM 1 GOM 2 GOM 3 Total waxes (% mass) 14.72 12.95 13.56CFPP (° C.) NF EN 116 −6 −5 −7 CPP (° C.) NF-T60-105 −15 −12 −12 CP (°C.) NF EN 23015 −7 −5 −5 MV15 (kg/m³) NF EN ISO12185 826.5 829.23 824.77Sulphur content (mg/kg) 18.6 7.80 7.10 Monoaromatics (% mass) 19 15.715.7 NF EN 12916 Diaromatics (% mass) 4 2 1.8 NF EN 12916 Triaromatics(% mass) 0.3 0.5 0.5 NF EN 12916 Total aromatics (% mass) 23.3 18.2 18NF EN 12916 Polyaromatics (% mass) 4.3 2.5 2.3 NF EN 12916 DistillationASTM D86 (° C.)  0% 157.2 158.6 161.5  5% 178.7 183.7 183.9  10% 186.9194 193.3  20% 207.9 215.4 211.9  30% 229.9 236.1 229.7  40% 250.1255.60 248.1  50% 266.9 273.6 264  60% 282 289.1 277.9  70% 298.1 303.7291.1  80% 315.5 319.5 306.7  90% 337.5 337.1 326.9  95% 353.5 350 343.6100% 356.9 358.6 354.5 MEVO content (% vol) 0 5 0

1. Modified alkylphenol-aldehyde resins obtained by a Mannich reactionof an alkylphenol-aldehyde condensation resin, comprising: at least onealdehyde and/or one ketone having 1 to 8 carbon atoms; and at least onehydrocarbon compound having at least one alkylmonoamine oralkylpolyamine group (alkylamine) having between 4 and 30 carbon atoms;the alkylphenol-aldehyde condensation resin obtained by condensation; ofat least one alkylphenol substituted by at least one linear or branchedalkyl group having 1 to 30 carbon atoms; and at least one aldehydeand/or one ketone having 1 to 8 carbon atoms.
 2. The resins according toclaim 1, which are obtained from at least one alkylphenol substituted inpara position.
 3. The resins according to claim 1, which are obtainedfrom at least one aldehyde and/or a ketone chosen from formaldehyde,acetaldehyde, propionaldehyde, butyraldehyde, 2-ethyl hexanal,benzaldehyde, or acetone.
 4. The resins according to claim 1, which areobtained from at least one alkylamine having at least one primary aminegroup.
 5. The resins according to claim 1, which are obtained fromp-nonylphenol, formaldehyde and at least one hydrocarbon compound havingat least one alkylmonoamine or alkylpolyamine group.
 6. The resinsaccording to claim 1, which are obtained from at least one alkylaminewith an aliphatic chain or a mixture of alkylamines with an aliphaticchain.
 7. The resins according to claim 1, with a viscosity at 50° C.measured using a dynamic rheometer with a shear rate of 100 s⁻¹ on asolution of the resin diluted with 30% by mass of an aromatic solventcomprised between 1,000 and 10,000 mPa·s.
 8. A method of improving thelow-temperature properties of motor fuels and hydrocarbon liquid fuels,the method comprising using one or more resins as additives, the resincomprising: at least one aldehyde and/or one ketone having 1 to 8 carbonatoms; and at least one hydrocarbon compound having at least onealkylmonoamine or alkylpolyamine group (alkylamine) having between 4 and30 carbon atoms; the alkylphenol-aldehyde condensation resin obtained bycondensation: of at least one alkylphenol substituted by at least onelinear or branched alkyl group having 1 to 30 carbon atoms; and with atleast one aldehyde and/or one ketone having 1 to 8 carbon atoms.
 9. Themethod according to claim 8, further comprising improving the dispersionof waxes and/or for limiting the settling of waxes in at least one of:motor fuels and the liquid fuels, based on hydrocarbon oils and middledistillates the boiling temperature range of which is in the majoritycomprised between 100 and 500° C.
 10. The method according to claim 8,wherein the fuels have a boiling range from 120 to 500° C.
 11. Acomposition of motor fuels and liquid hydrocarbon fuels the compositioncomprising, a boiling temperature range of the fuel being in themajority comprised between 100 and 500° C. comprising: a majorityproportion of hydrocarbon compounds and/or vegetable and/or animal oilsand/or their esters of oils and/or biodiesels of animal and/or vegetableorigin; and a minority proportion of at least one of the resin; at leastone aldehyde and/or one ketone having 1 to 8 carbon atoms; and at leastone hydrocarbon compound having at least one alkylmonoamine oralkylpolyamine group (alkylamine) having between 4 and 30 carbon atoms;the alkylphenol-aldehyde condensation resin: of at least one alkylphenolsubstituted by at least one linear or branched alkyl group having 1 to30 carbon; and with at least one aldehyde and/or one ketone having 1 to8 carbon atoms.
 12. The resins according to claim 1, wherein thealdehyde and/or ketone have 1 to 4 carbon atoms.
 13. The resinsaccording to claim 2, which can be obtained from p nonylphenol.
 14. Theresins according to claim 3, which can be obtained from at leastformaldehyde.
 15. The resins according to claim 4, which can be obtainedfrom at least one compound, all the amine groups of which are primaryamines.
 16. The resins according to claim 6, wherein the alkylamine(s)have a number of carbon atoms between 12 and
 24. 17. The resinsaccording to claim 7, wherein the viscosity is comprised between 1,500and 6,000 mPa·s.
 18. The method according to claim 10, wherein themotors fuels and/or fuels have a boiling range from 140 to 400° C. 19.The method according to claim 10, wherein the resins are incorporated inat least one of: jet fuels, gas oils or diesel motor fuels, fuel oildomestic, or heavy fuel oils.
 20. The compositions according to claim11, comprising between 5 and 5,000 ppm by mass of at least one of theresins.